Method of producing butadiene from petroleum and petroleum fractions



Patented Aug. 1, 1950 METHOD OF PRODUCING BUTADIENE FROM PETROLEUM AND PETROLEUM FRAC- TIONS Arno Brasch, New York, N. Y., assignor, by mesne assignments, to Electronized Chemicals Corporation, a corporation of Delaware No Drawing. Application October 9, 1945,

Serial No. 621,367

19 Claims.

My present invention relates to methods of producing butadiene from petroleum and fractions thereof and is disclosed in my prior U. S. patent applications Serial No. 442,136, filed May 7, 1942, which has become abandoned, for Method of Manufacturing Synthetic Rubber and Devices Therefor; Serial No. 442,137, filed May 7, 1942, which has become Patent Number 2,429,217, for Devices for Treatment of Matters with High Speed Electrons; Serial No. 442,138, filed May 7, 1942, which has become abandoned, for Method for Treatment of Matter; Serial No. 450,923, filed July 14, 1942, which has become abandoned, for Method and Means for Treatment of Perishable Substances and Products so Obtained; Serial No. 451,370, filed July 17, 1942, which has become abandoned, for Method and Means for Treatment of Vegetative Substances and Products so Obtained; Serial No. 487,179, filed May 15, 1943, which has become abandoned, for Process for Cracking Hydrocarbons by Means of Ultra High Speed Electrons; and Serial No. 488,278, filed May 24, 1943 which has become abandoned, for Preparation and Cracking of Hydrocarbons and Other Chemical Compounds by Means of Ultra High Speed Electrons to Obtain Rubber Starting Materials. Accordingly, the present patent application is a continuation in part of my above patent applications.

It is an object of my present invention to produce butadiene from petroleum and fractions thereof in a simple and inexpensive way.

It is a further object of my present invention to produce butadiene in such a manner that a great proportion of the petroleum fractions serving as initial materials are transformed into butadiene.

Still another object of my present invention consistsin methods of obtaining butadiene from petroleum and fractions thereof without use of very high temperature and/or pressure as commonly employed for cracking purposes and without use of rather expensive active catalysts used in known processes of this type.

With the above objects in view, my present invention mainly consists in processes of producing butadiene from petroleum and/or fractions thereof comprising cracking of the same by bombarding the petroleum and/or their fractions with high speed electrons resulting in decomposition of the high speed electron bombarded petroleum and/or petroleum fractions and formation of butadiene. I g

The term high speed electrons, as used above and in the following description and claims, is

' such a manner that each of these repeated electron bombardments lasts less than 10*, preferably less than 10- of a second. Despite the fact that the duration of each individual electron bombardment is extremely short, averaging about 10- to 10- of a second, the energy displayed is tremendous due to the fact that the whole energy accumulated in a condenser battery will be discharged and with the aid of the special tube will be converted into correspondingly high amounts of electronic radiation. If, for instance, the impulse generator will be charged and discharged over the discharge tube 30 times per minute and assuming that the end capacity of the generator is 8,000 centimeters and the voltage 15,000,000 volts, then an average electronic output of several thousand kilowatts will be obtained.

I have found that by using such short bombardment periods, it is possible to avoid almost entirely the formation of undesired unusable by-products. This is of great importance since in the commonly employed processes of producing butadiene a great percentage of the formed reaction products are such undesired substances, i. e. um usable by-products, and this constitutes the basic disadvantage of all known processes.

The following petroleum fractions can be used as starting materials for the production of butadiene: paraffin base, paraflin intermediate base, intermediate paraflin base, intermediate base, intermediate naphthene base, naphthene in- First of all, with my new process it is easily possible to obtain the very great energy necessary to achieve the desired conversion of petroleum into butadiene. This great energy can be produced without the application of heat and/or pressure, i. e, in a simple way. It is also evident that the treatment with high speed electrons cannot only be carried out without diiii ferent reactions in the electron bombarded petroleum and/or petroleum fractions; this in turn makes it possible to obtain higher yields of butadiene, a smaller percentage of undesired by-prodnets and consequently easier purification of the resulting butadiene.

Third, by producing butadiene in the way proposed by me, namely by treating petroleum and/or petroleum fractions with high speed electrons, it is possible to avoid the use of exof them described pensive active catalysts and apply so-called contact materials of the t below. lysts and also to simplify the construction of the apparatus for carrying out the cracking processes and producing butadiene.

Fourth, by eliminating heat treatment and use of active catalysts, it is possible to construct the various reaction vessels and chambers of nonexpensive metals instead of the heat and chemically resistant high grade alloy steels needed for thesepurposes so far.

I have found that it is advantageous to treat certain petroleum fractions in the vapor phase, since in this way it is possible to obtain exit gases which are very rich in mono-oleflnes and di-oleflnes; such olefln'es subjected to repeated electron bombardments give a high yield of butadiene.

A typical composition of such an exit gas is the following: About 9 to 16 per cent of hydrogen, methane, ethane and propane, about 24 to 28 per cent of lower molecular oleflncs, about 14 to 17 per cent of-butene, about to 12 per cent of aromatics and about 36 to 39 per cent of butadiene. Thus, it is possible to achieve by my present invention a series of reactions which tend to transform nearly all initial components of the petroleum and/or petroleum fractions into monooleflnes, di-oleflnes and of course also into butadiene.

I wish to emphasize, however, in this connection that my present invention is by no means. limited to the cracking of petroleum fractions,

since it is of course also possible to produce by this process butadiene from various petroleums themselves or from compounds which are formed during various processing operations of petroleum and/or petroleum fractions. Such compounds are for instance hydrocarbons, such as cyclohexane, cyclopentane and their derivatives, paraflln waxes, tank and still bottoms and various naptha cuts. Thus, using cyclohexane as initial material in my above described processes, it is possible to obtain a yield of pure butadiene amounting to up to 95% of the theoretical yield;

periods caused by the single consecutive electron bombardments. It is evident that no advantage would be attained by keeping the periods of bombardment extremely short if between these short periods the once started reactions would in part In this way, it is possible to save cataautomatically continue due to the initiation of chain reaction. In order to be able to regulate the length of-the reaction periods, I have found it advisable to add, e. g. admix to the initial materials to be electron bombarded, a small percentage of agents which are adapted to prevent or at least to retard continuation of the reactions caused by the electronic bombardment after discontinuation and termination of the same. I have found that such materials called by me contact mater have a double eflect, namely they not only retard continuation of the reaction after termination of the bombardment period but they also facilitate the energy distribution durr ing the bombardment without being catalytically active.

I have found that for the purposes of my present invention as contact materials I may very well use various metal oxides whichv are not only inexpensive but also available in large amounts. In accordance with -a preferred embodiment of my invention, I use in my new process as contact materials oxides of the metals of the second, third and fourth group of the periodic system, for instance, magnesium, zinc, aluminum, silicon and others.

A very material disadvantage of the use of catalysts in known processes lies in the inavoidable secondary reactions as incurred under the conditions of the standard pyrolytic processes that lead to the formation of oily polymerization products. These soon lower the activity of the catalysts so markedly that a reactivation is necessary, the oily polymers poisoning the entire active surface of the catalyst. Additional poisoning is caused by the formation of pyrolytic decomposition products due to the necessary high temperatures in standard cracking processes. Whereas the first inactivation is'reversible, the second one is irreversible,- thus completely destroying the activity of that part of the catalysts.

It should also be stressed that in accordance with my present invention it is necessary to use only a very small percentage of the contact material, not more than 10% ofthe weight of the reaction mixture. Contrary thereto, in known cracking processes it is necessary to use a great amount of highly active expensive catalysts. Compared with such known processes, the percentage of contact materials used in my processes is extremely small, not more than a few per cent of the amount of highly active catalysts being needed for thermal cracking processes. In ad dition thereto, it should be stressed that since these contact materials do not participate in the cracking reactions, their life is much longer than that of the catalytically active catalysts used to date.

I wish to stress again that the contact materials used for the purposes of the present invention serve a dual purpose, namely while the] formedmono-oleflnes and ,di oleiines, after termination of the high speed electron bombardment, it is possible to obtain a small number of well defined reaction products, particularly butathe types described above.

While I have described the invention as embodied in processes of producing butadienefrom petroleum and petroleum fractions, I do not intend to be limited to the details shown, since various modifications and changes may be made without departing in any way from the spirit of my invention.

Without further analysis, the foregoing will so fully reveal the gist of my invention that others can by applying current knowledge readily adapt it for various applications without omitting fea- 6. Method of producing butadiene from a substance selected from the group of petroleum and fractions thereof comprising cracking said substance by subjecting it to repeated bombardments with high speed electrons of a velocity equivalent to more than 2 million volts, each of said electron bombardments lasting less than of a second. in the presence of a.contact material not participating in the chemical reaction caused by said electron bombardment but facilitating said chemical reaction during said electron bombardtures that, from the standpoint of prior art,

fairly constitute essential characteristics ofthe generic or specific aspects of this invention and, therefore, such adaptations should and are intended to be comprehended within themeaning and range of equivalence of the following claims.

What I claim as new and desired to secure by Letters Patent is: x

1. Method of producing butadiene from a substance selected from the group of petroleum and fractions thereof comprising cracking said substance by repeatedly treating it during consecutive periods with high speed electrons of a velocity equivalent to more than one million volts, each of said consecutive periods lasting less than 10- of a second, thereby decomposing said substance and forming butadiene.

2. Method of producing butadiene from a substance selected from the group of petroleum and fractions thereof comprising cracking said substance by repeatedly bombarding it with high speed electrons, each of said electron bombardments lasting less than 10- of a second, decomposing thereby said substance and forming butadiene.

3. Method of producing butadienefrom a sub- V stance selected from the group of petroleum and fractions thereof comprising cracking said substance by subjecting it to repeated treatments with high speed electrons of a velocity equivalent to more than 2 million volts, each of said treatments lasting less than 10- of a second, thus de composing said substance and forming butadiene.

4. Method of producing butadiene from a substance selected from the group of petroleum and fractions thereof comprising cracking said substance by treating it repeatedly during a series of very short bombardment period with high speed electrons in the presence of a contact material not participating in the chemical reaction caused by said treatment but facilitating said chemical reaction during said treatment and retarding continuation of said chemical reaction after said treatment has been discontinued.

5. Method of producing butadiene from a substance selected from the group of petroleum and fractions thereof comprising cracking said substance by repeatedly treating it during consecutive periods withhigh speed electrons of a velocity ment and preventing continuation of said chemical reaction after said electron bombardment has been terminated, decomposing thereby said substance and forming butadiene.

'7. Method of producing butadiene from'a substance selected from the group of petroleum and fractions thereof comprising cracking said substance by combining it with sulphur and bombarding said mixture repeatedly during a series of very short bombardment periods with high speed electrons whereby the said substance present in said mixture is decomposed and butadiene is formed.

8. Method of producing butadiene from a substance selected from the group of petroleum and fractions thereof comprising cracking said substance by bombarding it repeatedly during a series of very short bombardment periods with high speed electrons in the presence of nitrogen, thereby decomposing said substance and forming butadiene.

9. Method of producing butadiene from a substance selected from the group of petroleum and fractions thereof comprising cracking said substance by bombarding it repeatedly during a series of very short bombardment periods with high speed electrons at a temperature atwhich said substance is in the gaseous state whereby said substance is bombarded in the gaseous phase and decomposed, resulting in formation of butadiene.

10. Method of producing butadiene from a substance selected from the group of petroleum and electron bombardment but facilitating said chemical reaction during said electron bombardment and retarding continuation of said chemical reaction after said electron bombardment has been discontinued.

- 11. Method of producing butadiene from a substance selected from the group of petroleum and fractions thereof comprising cracking said substance by bombarding it with high speed electrons in the presence ;of a contact material selected from the group of metals consistingof zinc, magnesium, aluminum, boron, calcium, strontium and silicon, said contact material not participating in the reaction caused by said electron bombardment but facilitating said reaction during said electron bombardment and retarding continuation of said reaction after said electron bombardment has been discontinued.

12. Method of producing butadiene by bombarding cycle-hexane and its naturally occurring alkyl-derivatives repeatedly during a series of very short bombardment periods with high speed electrons of a velocity equivalent to more than one million volts, thereby cracking said cycle-hexane tenes comprising cracking said n-butenes by repeatedly bombarding the same during consecutive bombarding p riods with high speed electrons of a velocity equivalent to more than one million volts, each of said consecutive bombarding periods lasting less than 10- of a second, thereby decomposing n-butenes and forming butadiene.

14. Method of producing butadiene from 1 and 2 n-butenes comprising cracking said 1 and 2 n-butenes by subjecting the same to repeated treatments with high speed electrons of a velocity equivalent to more than 2 million volts, each of said treatments lasting less than 10 of a second, thus decomposing said n-butenes and forming butadiene.

15. Method of producing butadiene from lawtenes comprising cracking said butenes by repeatedly bombarding the same durin a series of extremely short irradiation periods with high speed electrons at a temperature of between 100 and 150 C., thereby decomposing said butenes and forming butadiene.

16. Method of producing butadiene comprising cracking n-butenes by bombarding the same repeatedly during a series of extremely short irradiation periods with high speed electrons thus forming a mixture comprising butadiene and aromatic substances, removing said aromatic substances and bombarding the same repeatedly with high speed electrons, thus transforming the same thereby decomposing said butenes and forming 4 butadiene.

18. Method of forming butadiene from 2,3 dichloro-n-butene comprising dehydrochlorinating the same by repeatedly bombardin them during consecutive very short bombarding periods with Number high speed electrons in the presence of a contact material not participating in the chemical reaction caused by said electron bombardment but facilitating said chemical reaction during said electron bombardment and retarding continuation of said chemical reaction after said electron bombardment has been discontinued.

19. Method of producing butadiene from 2,3 dichloro-n-butene comprising the steps of bombarding said 2,3 dichlcro-n-butene repeatedly during a series of extremely short irradiation periods with high speed electrons at a temperature of between and 0., thus transforming said 2,3 dichloro-n-butene into a mixture of mono-chloro-butenes, purifying said monochloro-butenes and bombarding the same repeatedly with high speed electrons at a temperature of between and C. in the presence of a contact material not participatin in the chemical reaction caused by said electron bombardment but facilitating said chemical reaction during said electron bombardment and retarding continuation of said chemical reaction after said electron bombardment has been discontinued.

ARNO BRASCH.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date 1,906,402 Newton May 2, 1933 1,961,493 Hillis June 5, 1934 2,043,733 Bra-sch et al June 9, 1936 2,099,327 Brasch et a1 Nov. 16, 1937 FOREIGN PATENTS Number Country Date 154,213 Great Britain Apr. 24, 1922 299,735 Great Britain Oct. 30, 1928 OTHER REFERENCES Ind. Eng. Chem., pp. 1396-1398, December, 1931. 

7. METHOD OF PRODUCING BUTADIENE FROM A SUBSTANCE SELECTED FROM THE GROUP OF PETROLEUM AND FRACTIONS THEREOF COMPRISING CRACKING SAID SUBSTANCE BY COMBINING IT WITH SULPHUR AND BOMBARDING SAID MIXTURE REPEATEDLY DURING A SERIES OF VERY SHORT BOMBARDMENT PERIODS WITH HIGH SPEED ELECTRONS WHEREBY THE SAID SUBSTANCE PRESENT IN SAID MIXTURE IS D ECOMPOSED AND BUTADIENE IS FORMED. 